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A Study of Optically Active Dyes 


BY 

ARTHUR WILLIAM INGERSOLL 


B. S. University of Nebraska, 1917 
M. S. University of Nebraska, 1918 


THESIS 

Submitted in partial fulfillment of the requirements for the degree of 
Doctor of Philosophy in Chemistry in the Graduate School 
of the University of Illinois, 1922 


Reprinted from the Journal of the American Chemical Society 
Vol. XLIV, No- 12. December, 1922 





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A Study of Optically Active Dyes 


BY 

ARTHUR WILLIAM INGERSOLL 

i| 

B. S. University of Nebraska, 1917 
M. S. University of Nebraska, 1918 


THESIS 

Submitted in partial fulfillment of the requirements for the degree 
Doctor of Philosophy in Chemistry in the Graduate School 
of the University of Illinois, 1922 


Reprinted from the Journal of the American Chemical Society 
Vol. XLIV, No. 12. December, 1922 





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[Reprinted from the Journal of the American Chemical Society, 
Vol. XUV, No. 12. December, 1922.] 


[Contribution from the Chemical Laboratory of the University of Illinois] 
OPTICALLY ACTIVE DYES. I 
By A. W. Ingersoll with Roger Adams 1 

Received August 14, 1922 

The nature of the action by which dyes are absorbed and more or less 
permanently held by animal or vegetable fibers, has been the subject of a 
large number of investigations. The first work recorded was during the 
eighteenth century and since then the experiments in this field have been 
very extensive. 2 From results so far obtained, no definite conclusions can be 
drawn as to whether there is involved a physical or chemical phenomenon 
or both. Scores of articles have been published by many authors, some 
of whom are advocates of a physical, some of a chemical explanation. 

An excellent method which should throw light upon this subject is the 
study of the action of optically active dyes upon fibers. Each of a pair 
of mirror images would be expected to have the same dyeing properties, 
if the absorption by the fibers is purely a physical process. On the other 
hand, if a chemical reaction of any sort is taking place when the dye is 
absorbed, a different degree or rate of absorption of the d and l forms 
might take place on account of the optical activity of the substances of 
which the fibers are composed. In this connection, however, it must be 
considered that even though the dyeing process may be a chemical one, 
the d and l forms of every pair of dyes would not necessarily be absorbed 
to a different degree, sufficient to be measured. Only after the study of a 
large number of such pairs could a convincing conclusion be drawn. 

Very little work upon the selective absorption of one active compound 
as compared with its enantiomorph has been carried out and no pairs of 
optically-active dyes have been made. In 1904, Willstaetter 3 discussed 
the possibility of selective absorption by wool of one active component 
of a racemic mixture. He carried out experiments upon solutions of 

1 This communication is an abstract of a thesis submitted by A. W. Ingersoll in 
partial fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry 
at the University of Illinois. 

2 An excellent review of the articles on the theory of dyeing from the earliest times 
may be found in the following books: Georgievics, “Chemistry of Dyestuffs,” Scott, 
Greenwood and Co., 1903; Dreaper, “Chemistry and Physics of Dyeing,” P. Rlakiston’s 
Son and Co., 1906; Knecht, Rawson and Loewenthal, “A Manual of Dyeing,” Charles 
Griffin and Co., 1910; Wood, “Chemistry of Dyeing,” D. Van Nostrand Co., 1913. 

3 Willstaetter, Ber.. 37, 3758 (1904). 


OPTICAL!/Y ACTIVE DYES 


2931 


racemic alkaloids, but in no case was evidence of selective absorption 
found. Unsuccessful attempts to prepare optically active dyes are re¬ 
ported by Mayer, 4 Meisenheimer 5 and Longobardi. 6 

An interesting paper by Porter and Hirst 7 has appeared in which a 
number of dyes containing an asymmetric carbon atom are described. 
These were made by the diazotization and coupling of aminodiphenyl 
alkyl carbinols. No experiments are described on the selective absorp¬ 
tion of a single form by wool although the authors state that certain 
qualitative results serve to indicate selective absorption. The resolution 
of the dyes was not accomplished. 

In studying the mechanism of dyeing by this general method, there are 
many reasons why it would be a distinct advantage to work with the pure 
d and l forms of various dyes in preference to the racemic modifications. 
With the latter, selective absorption of one form could be found only by 
determination of the rotation of the resulting solution after dyeing had 
taken place. Not only does the determination of the rotation of a deeply 
colored solution present difficulties, but if, as it might happen in many 
cases, the difference in the rate of absorption of one form was only slightly 
different from that of the other form, the rotation of the resulting solution 
might be so small that it could not be determined. This would be especially 
true if the rotation of the pure dyes was small, a possibility which must 
not be overlooked. If, however, the pure d and l forms of the dye were 
available, a comparison of two equivalent solutions as regards absorption 
could be made by taking a colorimeter reading on the partially exhausted 
d and l dye solutions and comparing them with the original solutions. 
Very accurate data could thus be obtained. The rotation of the partially 
exhausted racemic dye solutions could be used merely as a method of 
checking the other results. 

In considering a procedure for obtaining d and l dyes in a pure state, 
the methods first thought of are: (1) preparation of a dye containing an 
asymmetric carbon atom and in addition a group which will allow the 
effecting of its resolution; (2) the resolution of an intermediate containing 
an asymmetric carbon atom and, in addition, a group through which it 
could be converted into dyes. The first method seems less promising 
because of the probable difficulties in resolution. Even the second method 
would probably require extensive experiments before the active forms 
were obtained; moreover, the chances are that only one form could be 
obtained pure. Without both forms of the dyes in a pure state, results 
from the dyeing experiments would be of little value. 

The better method of approach for the preparation of numerous pairs of 

4 Mayer, Atti accad. Lincei [V] 23, 353 (1914). 

6 Meisenheimer, Ann., 423, 105 (1921). 

6 Longobardi, Anales soc. quint. Argentina, 8,^153^(1920); C. A., 15, 3984 (1921). 

7 Porter and Hirst, This^Journa!, 41, 1264 (1919). 


2932 


A. W. INGERSOLD WITH ROGER ADAMS 


optically active dyes in the least time and with a minimum amount of 
experimentation, is a modification of the second procedure just mentioned. 
Known pairs of any d and l compounds are sought where the racemic 
modifications are readily made, where the methods of resolution are 
thoroughly worked out, and in which certain groups exist that will allow 
the conversion of the substances into dyes by one or more easy steps. 
There is no class of compounds which will fulfil the above conditions as 
satisfactorily as the amino acids or amino esters. Many have been ex¬ 
tensively studied in regard to preparation and resolution with isolation 
of both d and l forms in a pure state. Moreover, many of them possess 
high rotations which allow with certainty the formation of dyes with 
comparatively large rotations. The best of all of the amino acids for this 
work is phenyl-amino-acetic acid which has been used exclusively in this 
preliminary investigation. It is readily made, readily resolved, and has a 
high rotation. One of the most convenient methods for converting the 
amino acids to dyes is represented below and in the Laboratory has proved 
very satisfactory. 

(p) N0 2 C 6 H 4 COCl 6H HN0 2 + HC1 

RCHC0 2 H-RCHC0 2 H —^ RCHC0 2 H-> 

I I I 

NH 2 NHC0C 6 H4N0 2 NHCOCelLNHa 

RCHC0 2 —>- dyes 

NHC0C 6 H 4 N 2 C1 

As yet the investigation is only in its early stages. Two pairs of dyes 
have been made, namely, those produced by starting with the dextro and 
levo forms of phenyl-amino-acetic acid and carrying out with each the 
series of reactions just described, coupling with /3-naphthol in one case 
and with dimethylaniline in the other. The proper light for use in ob¬ 
taining accurate rotations of these dyes has not yet been determined. It 
was possible to get readings of the pair of /3-naphthol dyes using sunlight, 
but very accurate readings cduld not be obtained. No readings could be 
obtained with the dimethylaniline dyes using sunlight. The dimethylan¬ 
iline dyes were certainly active, however, since on making an equal 
mixture of the d and l forms, a product of different melting point was 
produced. 

Only preliminary dyeing experiments have been carried out, and these 
on wool. Quantitative amounts of equivalent standard solutions of d 
and l forms were treated under like conditions with the same amounts of 
wool. From time to time samples of the dye solutions were pipetted out 
and the relative concentrations determined with a colorimeter. The 
results show that the d- and /-/?-naphthol dyes were absorbed in the same 
relative amounts over short as well as long periods of time. On the other 
hand, the preliminary experiments on the 2 dimethylaniline dyes indicated 
that one is absorbed more rapidly than the other. Several other pairs 




optically active) dyks 


2933 


of dyes, of which some are basic and some acid, are being prepared. The 
absorption spectra, rotation, and other constants are now being accurately 
determined. A discussion of the conclusions as to whether the evidence 
is for chemical combination or adsorption is being reserved till more 
accurate experimental data are available. 

Experimental 

d/-Phenyl-amino-acetic Acid.—The phenyl-amino-acetic acid was made by the 
method of C. S. Marvel and W. A. Noyes 8 by the interaction of sodium cyanide, am¬ 
monium chloride and benzaldehyde. A few slight changes were made as follows: 
ethyl alcohol in place of methyl alcohol was used as a medium for the initial condensation; 
the time of hydrolysis of the nitrile was increased from 2 to 8 hours; the crude phenyl- 
amino-acetic acid after air drying was heated on a steam-bath for 15 minutes with ap¬ 
proximately an equal weight of benzene. This treatment caused the water to separate 
as a layer under the benzene and at the same time dissolved a large amount of dark- 
colored impurity. After filtration and drying, the phenyl-amino-acetic acid was pure 
enough for use in this investigation. 

d - and /-Phenyl-amino-acetic Acid.—The phenyl-amino-acetic acid was resolved to 
yield pure /-product and impure d-product by the method of Betti and Mayer, 9 the 
fractional crystallization of the d-camphor sulfonate of the racemic modification. This 
process is a very convenient one. From 151 g. of pure d/-phenyl-amino-acetic acid and 
245 g. of pure d-camphor sulfonic acid in 800 cc. of boiling water, 150 g. of pure /-phenyl- 
amino-acetic acid d-camphor sulfonate crystallized upon slow cooling of the solution. 
By concentration of the filtrate from these crystals and repeated fractionation, the yield 
of pure product was increased to over 90%. The sirupy mother liquors contained im¬ 
pure d-phenyl-amino-acetic acid d-camphor sulfonate. By hydrolysis of these salts with 
ammonia pure /-phenyl-amino-acetic acid was obtained and d-phenyl-amino-acetic acid 
of about 90% purity. The d form was completely purified by the method of Fischer 
and Weickhold. 10 The rotations of the d and / forms used in the preparation work were 
as follows. 

/-Phenyl-amino-acetic Acid. Subs., 3.8364: made up to 50 cc. with a mixture of 

34.54 cc. of N HC1 and 15.46 cc. of H 2 0 at 20° gave a rotation of —22.75° in a 2dcm. 
tube with sodium light; [a] 2 © =—157.5°. 

d-Phenyl-amino-acetic Acid. Subs., 1.6161: made up to 50 cc. with a mixture of 

14.55 cc. of N HC1 and 6.51 cc. of H 2 0 at 20° gave a rotation of +22.84° in a 2dcm. 
tube with sodium light; [a]^ = +158.0°. 

^-Nitrobenzoyl Chloride.—^-Nitrobenzoyl chloride was made from ^-nitrobenzoic 
acid and phosphorus pentachloride. * 11 

d/-Phenyl(£-nitrobenzoylamino)acetic Acid.—H0 2 CC(C 6 H 6 )HNHC0C6H4N0 2 .—A 
solution of 30.2 g. (1 mole) of pure phenyl-amino-acetic acid was dissolved in 240 cc. 
of 10% sodium hydroxide solution and then made up to a total volume of 500 cc. with 
water. Thirty-two g. (2 mole) of sodium bicarbonate was then added, thus causing a 
part of the amino acid to precipitate. Finally, 40 g. (1.1) mole of pure, finely powdered 
^-nitrobenzoyl chloride was added and the mixture vigorously agitated with a me¬ 
chanical stirrer for 40 to 50 minutes. During this procedure the mixture was kept 
below 20° by cooling, since the condensation product is rather easily decomposed by 

8 Marvel and Noyes, This Journal, 42, 2264 (1920). 

9 Betti and Mayer, Ber., 41, 2071 (1908). 

10 Fischer and Weickhold, ibid ., 41, 1286 (1908). 

11 “Organic Syntheses,” II, John Wiley and Sons. 



2934 


A. W. INGERSOIX WITH ROGER ADAMS 


warm alkali. At the end of this time the amino acid and practically all of the p- nitro- 
benzoyl chloride had gone into solution and a deep purple color had developed. The 
solution was filtered, thus removing any undissolved material, and an excess of 10% 
hydrochloric acid was cautiously added. The purple color was discharged and a pink, 
rather sticky solid was precipitated. Without filtering, this solid product was allowed to 
stand and stirred occasionally with a glass rod until after several hours it became 
flocculent and nearly white. It was then filtered from the solution. The product 
weighed when dry 54 to 58 g. (70 to 75%). After three crystallizations from 95% 
alcohol it was absolutely pure and formed pale yellow needles melting at 184° (corr.). 

From the alcoholic mother liquors from the crystallization, it was possible to re¬ 
cover a certain amount of the condensation product. There always was found, however, 
in these mother liquors a certain amount of the corresponding ester which formed during 
the crystallization. Consequently all product recovered in this way should be carefully 
tested for impurities before using. 

Analysis. Subs. 0.2000: 18.52 cc. of 0.07139 N HC1. Calc, for Ci 6 H 12 0 4 N 2 : 
N, 9.33. Found: 9.26. 

d/-Ethyl-phenyl(£-mtrobenzoylamino) Acetate, CVH 6 0 2 CC(C 6 H6)HNHC0C6H4N0 2 . 
—This substance was obtained in the mother liquors from the crystallization from alcohol 
of the above acid. It was also obtained by esterification of the acid with absolute ethyl 
alcohol and dry hydrogen chloride. The substance was purified by crystallizing from 
alcohol, after which it formed pale yellow needles melting at 140° (corr.). 

Analysis. Subs., 0.3000 : 25.5 cc. of 0.07138 N HC1. Calc, for Ci7H 16 0 6 N 2 : 
N, 8.5. Found: 8.5. 

d/-Phenyl(£-aminobenzoylamino)acetic Acid, H0 2 CC(C 6 H5)HNHC0C 6 H4NH3.— 
A solution of 20 g. of d/-phenyl(£-nitrobenzoylamino)acetic acid was dissolved in a slight 
excess of dil. ammonium hydroxide and the solution added to a hot solution of 120 g. 
(6.5 mole) of pure hydrated ferrous sulfate crystals in 300 cc. of water. To this hot 
mixture was then added in 20cc. portions during 10 minutes, 100 cc. of cone, ammonium 
hydroxide and the whole mixture heated for a half an hour on a steam-bath. The 
reduction proceeded rapidly, the dark green ferrous hydroxide being changed to the 
brown ferric hydroxide after each addition of ammonium hydroxide. After the reduc¬ 
tion was complete the mixture was filtered while hot, first with suction and then through 
a fluted filter. The filtrate was concentrated on a steam-bath under diminished pres¬ 
sure until a volume of 200 cc. remained. This was cooled and carefully acidified with the 
quantity of dil. hydrochloric acid calculated to liberate the free base. After standing 
for about an hour, the precipitated amino acid was filtered, washed with a little cold 
water and crystallized from about 600 cc. of boiling water. A small amount of yellow 
insoluble oil was almost invariably present but was readily removed by filtration of the 
hot solution. The yield of product after one crystallization amounted to 12-14 g. The 
substance at this point was almost always slightly yellow and two additional crystalliza¬ 
tions using bone black were necessary in order to leave the substance pure white. The 
compound melted at 152° (corr.). 

Analyses . Subs., 0.3000, 0.3000: 30.48, 30.48 cc. of 0.07138 N HC1. Calc, for 
Ci 5 Hi 4 03 N 2 : N, 10.4. Found: 10.2, 10.2. 

d/-Phenyl(/>-aminobenzoylamino) acetic Acid Hydrochloride, H0 2 CC(C 8 H b )HNH- 
C0C 8 H4NH 2 .HC1.—The hydrochloride of the amine was prepared by dissolving the 
base obtained after one crystallization in hot 1:1 hydrochloric acid and warming with 
bone black. The hot solution was filtered and cooled, whereupon white, hard needles 
precipitated. They melted with decomposition when heated slowly between 190° and 
200° but when immersed in a bath already heated, the decomposition was fairly'sharp 
at 215°. 


OPTICAIXY ACTIVE DYES 


2935 


Analyses. Subs., 0.5989, 0.6225: AgCl, 0.2760, 0.2875. Calc, for Ci*H« 03 N 2 C 1 : 
Cl, 11.56. Found: 11.40, 11.43. 

/-Phenyl(^nitrobenzoylamino)acetic Acid, H0 2 CC(C6H 5 )HNHC0C«H4N02.—This 
substance was prepared under exactly the same conditions as the corresponding racemic 
acid, using £-nitrobenzoyl chloride and /-phenyl-amino-acetic acid. The condensation 
product, however, was much more soluble in alcohol than the racemic modification and 
it was, therefore, necessary to crystallize from ethyl acetate in order to get the best 
results. When pure, the substance formed yellow needles melting at 163° (corr.). 
The yield of crude product was more than 90%. During crystallization of this com¬ 
pound, excessive concentration of the mother liquor in order to obtain a further yield 
of product was avoided since the small amount of alcohol which was present in the 
ethyl acetate readily caused esterification of the acid and this ester was always present 
in the mother liquors. 

Analyses. Subs., 2.0000: made up to 25 cc. in abs. ethyl alcohol at 20° gave rota¬ 
tion of —13.85° in 2dcm. tube with sodium light; [a] 2 o=—86.56°. Subs., 0.2000: 
18.56 cc. of 0.07138 N HC1. Calc, for Ci^OtNz: N, 9.3. Found: 9.3. 

/-Ethyl (£-nitrob enzoylamino) ac etic Acid, C2H 5 02CC(C6H 5 )HNHC0C«H4N02.— 
This ester was obtained from the mother liquors in the crystallization of the corre¬ 
sponding acid just mentioned above. 

It was also prepared by esterifying the acid with absolute alcohol and dry hydrogen 
chloride. After crystallizing from alcohol, the product formed yellowish needles which 
melted sharply at 155° (corr.). 

Analyses. Subs., 1.0150: made up to 25 cc. in CH 3 CO 2 C 2 H 6 (U. S. P.) at 20° gave ro¬ 
tation of —5.50° in 2 dcm. tube with sodium light; [a] 2 ^ = —67.7°. Subs., 0.2000,0.2000: 
17.07, 17.05 cc. of 0.01738 N HC1. Calc, for CnHieOeNa: N, 8.54. Found: 8.53. 

/-Phenyl (£-aminobenzoylamino) acetic Acid, H02CC(C6H 6 )HNHC0C 6 H4NH 2 .— 
This substance was prepared by the reduction of the corresponding /-nitro compound 
under exactly the same conditions as used for the racemic isomer. It was best purified 
by crystallizing from water in which it was slightly more soluble than the racemic modifi¬ 
cation. The yield was 65 to 70% after one crystallization, and it was essentially pure. 
The second and third crystallizations took the last traces of color from the compound 
but did not essentially change the melting point or rotation. The product formed large 
needles which melted sharply at 168-169° (corr.). 

Analyses. Subs., 2.0000: made up to 25 cc. in N HC1 at 20° gave rotation of 
—15.00° in 2 dcm. tube with sodium light; [a] 2 D =—93.75°. Subs., 0.2000: 20.60 cc. of 
0.07138 N HC1. Calc, for C 16 H 14 O 3 N 2 : N, 10.4. Found: 10.3. 

/-Phenyl (/>-aminobenzoylamino)acetic Acid Hydrochloride, H0 2 CC(C6H 6 )HNH- 
COC 6 H 4 NH 2 .HCI.—The hydrochloride was prepared from the base by cooling a hot 
solution of the amino compound in strong hydrochloric acid. White crystals were thus 
obtained which did not melt sharply, but decomposed when plunged into a melting- 
point bath held between 220° and 222°. 

Analyses. Subs., 0.5005, 0.5019: 14.76, 14.74 cc. of 0.1096 N AgNO s . Calc, for 
CieHifiOsNaCl: Cl, 11.56, Found: 11.47, 11.41. 

</-Phenyl(£-nitrobenzoylamino) acetic Acid, H02CC(C 6 H5)HNHCOC 6 H4N02.—This 
substance was obtained in exactly the same manner as the corresponding /-derivative, 
by condensing p-nitrobenzoyl chloride and d-phenyl-amino-acetic acid. The product 
had the expected physical and chemical properties which were identical with the /- 
compound. The same precaution was taken not to evaporate the mother liquors too 
far when crystallizing in order to avoid the contamination with ethyl ester. The sub¬ 
stance melted at 163° (corr.). 


2936 


A. W. INGERSODD WITH ROGER ADAMS 


Analyses. Subs., 2.0000: made up to 25 cc. in abs. ethyl alcohol gave rotation of 
+ 13.78° in 2 dcm. tube with sodium light; [«] 2 d = + 86.13°. Subs., 0.2000: 18.41 cc. of 
0.07138 N HC1. Calc, for CisH^O^: N, 9.33. Found: 9.20. 

d-Ethyl(£-nitrobenzoylamino)acetic Acid, QH 6 0 2 CC(C 6 H 5 )HNHC 0 CVEl 4 NH 2 .— 
This substance was obtained from the mother liquors from the crystallization of the d- 
acid and also by esterification by means of alcoholic hydrogen chloride. It melted at 
155° (corr.). 

Analyses. Subs., 1.1207: made up to 25 cc. in CH 3 CO 2 C 2 H 6 (U. S. P.) at 20° gave 
rotation of +6.04° in 2 dcm. tube with sodium light; [a ] 2 D 0 = + 67.4°. Subs., 0.3000, 
0.3000: 25.85, 25.65 cc. of 0.07138 N HC1. Calc, for CnHi 6 0 6 N 2 : N, 8.54. Found: 
8.62, 8.55. 

</-Phenyl(£-aminobenzoylamino)acetic Acid, H 02 CC(C 6 H 6 )HNHC 0 C 6 H 4 NH 2 .— 
This substance was prepared by the reduction of the d-nitro acid, as in the preparation 
of the corresponding /-compound. After two crystallizations from water the product 
was practically white and melted at 168-169° (corr.). 

Analyses. Subs., 2.0000: made up to 25 cc. in N HC1 at 20° gave rotation of 
+ 14.98° in 2 dcm. tube with sodium light; [«] 2 d = +93.63°. Subs., 0.2000: 20.62 cc. of 
0.07138 N HC1. Calc, for Ci 5 H 14 0 3 N 2 : N, 10.38. Found: 10.31. 

d-Phenyl(£-aminobenzoylamino) acetic Acid Hydrochloride, H0 2 CC(C6H fi )HNH- 
COC 6 H 4 NH 2 .HCI.—By warming the base with cone, hydrochloric acid and then cooling, 
the hydrochloride separated in hard, white needles. These melted with decomposition 
fairly sharply when dipped into a bath heated at 220 °. 

Analyses. Subs., 0.5041, 0.5015: 14.85, 14.80 cc. of 0.1096 N AgN0 3 . Calc, for 
Ci 5 H 16 0 3 N 2 Cl: Cl, 11.56. Found: 11.45, 11.47. 

Diazotization?offd/-Phenyl(£-ammobenzoylamino)acetic Acid and Coupling with 
/3-Naphthol, H 0 2 CC(C 6 H 6 )HNHCOQH 4 N 2 CioH 6 OH.—The base was dissolved in dil. 
hydrochloric acid, diazotized and coupled with /3-naphthol in potassium hydroxide 
solution in the usual way. After standing for about an hour at room temperature, the 
red jelly-like mass was strongly acidified with hydrochloric acid and the dye which pre¬ 
cipitated was filtered and dried. It was purified by crystallizing from boiling glacial 
acetic acid, in which it was soluble to the extent of about 2 g. in a liter. The yield was 
practically quantitative. The substance when pure formed small orange-red needles 
which melted sharply at 252°. It is readily soluble in alkalies and ammonium hydrox¬ 
ide but insoluble in water and organic solvents. 

Analysis. Subs., 0.1843: N 2 , 17.3 cc. (33°, 748 mm.). Calc, for C 2 6Hi 9 0 4 N»: 
N, 9.9. Found: 10.1. 

Diazotization of /-Phenyl (£-aminobenzoylamino) acetic Acid and Coupling with 
/3-Naphthol, H 0 2 CC(C 6 H 5 )HNHCOCeH 4 N 2 CioH 60 H.—The crude dye was washed a few 
times with cold glacial acetic acid in order to remove most of the water before crystalliza¬ 
tion. The product was nearly 10 times as soluble in glacial acetic acid as the racemic 
compound, and consequently was crystallized fairly readily. It formed orange-red 
crystals melting at 238°. The yield was 8.7 g. 

Analyses. Subs., 1.0000: made up to 50 cc. in water containing 1.1 equivalents 
of NaOH at 20° gave rotation of —1.09° with sunlight; [a] 25 = —27.25°. Subs., 0.2417: 
N 2 , 23.2 cc. (36°, 748.5 mm.). Calc, for C 26 H 19 04 N 3 : N, 9.9. Found: 10.1. 

Diazotization of </-Phenyl(£-aminobenzoylamino)acetic Acid and Coupling with 
/3-Naphthol, H0 2 CC(CeH6)HNHCOC6H4N 2 CioH60H.—The product looked and acted 
in identically the same way as the /-compound and melted sharply at 238° (corr.). 

Analyses. Subs., 1.0000: made up to 50 cc. in water containing 1.1 equivalents 
of NaOH at 20° gave a rotation of +1.14° in 2dcm. tube with sunlight; [a] 26 - +28.50°. 


OPTICALLY ACTIVE DYES 2937 

Subs., 0.2036, 0.1310: N2, 19.7 cc. (32°, 748 mm.), 12.1 cc. (30°, 747 mm.). Calc, for 
C25H19O4N3: N, 9.9. Found: 10.3, 10.0. 

Diazotization of /-Phenyl (£-aminobenzoylamino)acetic Acid and Coupling with 
Dimethylaniline, H0 2 CC(CVH5)HNHC0C6H4N 2 C8H 4 N(CH 3 )2.—The base was diazo- 
tized and coupled with dimethylaniline in the usual way. To the resulting solution, 
with mechanical stirring, 25 g. of crystallized sodium acetate was added in small portions, 
thus reducing the acidity to a point where coupling occurred and the dye separated 
from solution as a yellow-brown precipitate. It was filtered and crystallized from 1 liter 
of 50% alcohol. After three crystallizations the product, which formed red-brown 
needles, was pure and melted at 189-190°. 

An attempt was made to determine the rotation in absolute alcohol using sunlight 
but no readings could be obtained with this light. 

Analysis. Subs., 0.1994: N 2 , 23.3 cc. (33°, 751 mm.). Calc, for C23H22O3N4: N, 
13.92. Found: 13.80. 

Diazotization of d-Phenyl(^-aminobenzoylamino) acetic Acid and Coupling with 
Dimethylaniline, HOaCCCCWHNHCOCfl^NaCs^NtCHaV—The method of prepara¬ 
tion of this dye is identical with that for the /-isomer. It melted when pure at 188-189°. 
No rotation could be observed by the use of sunlight. 

Analysis. Subs., 0.3438: N*. 43.6 cc. (24°, 741 mm.). Calc, for C23H22O8N4: 
N, 13.92. Found: 13.80. 

The preparation of the d/-phenyl(£-aminobenzoylamino) acetic acid from dl- 
phenyl-amino-acetic acid presented difficulties. The product was not easy to crystallize 
and different melting points on different samples were obtained. Further study of this 
compound is being made. 

Summary 

1. Suitable methods for the preparation of various pairs of optically 
active dyes are discussed. 

2. A very convenient specific method is given for the preparation of 
optically-active dyes. It consists in starting with amino acids which have 
first been resolved by known methods and converting to dyes by the 
following series of reactions. 

RCHCO2H RCHCO2H RCHCO2H RCHCO2H 

—>- | —>■ | —> | —>- dyes 

NH 2 NHCOC6H4NO2 (p) NHCOC 6 H 4 NH 2 ( p ) ^HC 0 C 6 H 4 N 2 C 1 ( p ) 

3. Two pairs of optically active dyes have been prepared, namely, 
those starting with d- and /-phenyl-amino-acetic acid, and after carrying 
out the series of reactions just described, coupling with /3-naphthol and 
dimethylaniline, respectively. These pairs of dyes have been studied in 
only a preliminary way. The results tend to show that the /3-naphthol 
dyes are absorbed in equal amounts by wool, but that the dimethylaniline 
dyes are absorbed in different amounts during the same period of time. 

Urbana, Illinois 







i - <W 

* 














VITA 


The writer was born November 8, 1894, near Burr, Nebraska. 
He received his elementary education in the public schools of 
Otoe County, Nebraska, and in September, 1913, entered the 
University of Nebraska, where he received the degree of Bachelor 
of Science in Agriculture in 1917, and Master of Science in 
Chemistry in 1918. In 1917-18, he was Graduate Assistant in 
Chemistry in the University of Nebraska. From June to Decem¬ 
ber, 1918, he was in Chemical Warfare Service, U. S. Army. 
From January to September, 1919, he was Instructor in Chem¬ 
istry and Assistant in the Experiment Station, University of 
Nebraska. He entered the University of Illinois in September. 
1919, and has held the position of Graduate Assistant in Chem¬ 
istry during the years 1919-20, 1920-21 and 1921-22. 








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